Reaction of beta-lactone, alcohol and hydrogen halide



Patented June 24, 1947 ,UNI'TED REACTION OF BETA-LACTONE, ALCOHOL AND HYDROGEN HALIDE Thomas L. Gresham and Forrest w. Shaver,

Akron, Ohio, assignors to The B. I". Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application October 5, 1945, Serial No. 820,665

- .10 Claims. (01.260-487) This invention relates to the chemical reaction of a beta-lactone, an alcohol and a hydrogen halide, and pertains more specifically to the preparation of esters of beta-halo carboxylic acids, and esters of alpha-beta unsaturated carboxylic acids by this reaction.

It is disclosed in U. S. Patent 2,352,641 to Frederick E. Kiing that beta-lactones, that is, lactones or inner esters of beta-hydroxy carboxylic acids, such as beta-propiolactone (also called hydracrylic acid lactone) will react with alcohols such as ethyl alcohol to produce betaalkoxy carboxylic acids.

we have now discovered that the reaction or beta-lactones with alcohols takes an entirely dit- ..ierent course when a hydrogen halide is also present. In this event. an ester of a beta-halo carboxylic acid, rather than a beta-alkoxy carboxylic acid, is formed in accordance with the following equation:

a'oa xx c vc-c=o Alcohol Hydrohalide Beta-laotone I x-c----cc-on' mo Ester oi beta-halo carboxylic acid where R is an alcohol radical; x is a halogen atom such as chlorine, bromine, or iodine, preferably chlorine, and R is hydrogen or a substituent group.

when the ester formed contains a plurality of halogen atoms, as when a polyhydric alcohol or 1 a halogenated alcohol is usedjit is often unstable and loses one or more molecules of hydrogen halide when heated, with the result that an unsaturated ester is produced.

In carrying out the reaction no critical conditions are necessary and a variety of procedures may be employed. A preferred procedure consists in dissolving the beta-lactone in a molecular excess of the alcohol (it the latteris a liquid as is ordinarily the case), adding hydrogen halide to the solution in molecular excess over the betalactone preferably by saturating the solution with a stream of gaseous hydrogen halide for about 1 to 10 hours while the solution is cooled below room temperature, say to about 0 to 20 6.; refluxing the solution to complete the reaction, and then distilling the reaction product. Catalysts for the reaction, which are preferably but not necessarily present, include the halides of metals such as zinc chloride, aluminum chloride, ferric chloride, aluminum bromide, etc.

- Other procedures by which the alcohol, the beta-lactone and the hydrogen halide are brought into reactive contact with one another may also be used. For example, the hydrogen halide may be added, either in the gaseous ilormv or in water solution as the halogen acid, to the alcohol; the beta-lactone added and the solution refluxed and distilled, or the-hydrogen halide may be added to a solution of the beta-lactone in the alcohol, and the product then isolated without first refluxing the solution. Solvents for all or the reactants may be present but are generally em ployed only when the alcohol is a solid and will not itself dissolve the other reactants.

The practice oi! the invention may be illustrated by the following specific examples of the production of typical esters oi beta-halo propionic acids from an alcohol, a hydrogen halide and betapropiolactone.

Example 1 83.5 (1/38 mm., and identified as ethyl betachloropropionate, is obtained in about yield.

. Exdnvple 2 A solution consisting of 72 grams of betapropiolactone and 2 g. of'i'erric chloride dissolved in 200 ml. of commercial ethanol is prepared. This solution is cooled to 0 C., and while maintaining the temperature at about 0-10 0., hydrogen chloride is introduced for about 5'hours.

.The reaction mixture is allowed to warm to room temperature'; saturated with 'HCland allowed to stand overnight. It' is then pouredinto a large volume'otfice water and the'oll which separates is extracted with ether and'theethereal solution dried over sodium sulfate. The ,etheris removed leaving a residue which is 'redi'stilled to produce 68.3 grams (52.1%) of substantially pure ethyl w beta-chloropropionate.

I Example 3 '72 grams of beta-propiolactone are added to 300 ml. of a solution of hydrogen chloride inethanol ata temperature or 246 C. Hydrogen chloride is also passed into the solution during the addition to keep the solution saturated with HCl. The reaction mixture is refluxed for about 6 hours and then distilled. 86.3 g. (63.2%) of ethyl beta-chloropropionate are thus obtained.

' Examples 4 and s The procedure oil-Example 3 is repeated except that n-butanol is employed in place of ethanol. N-butyl beta-chloropropionate (B. P.

. 76.8-77.8/6mm; N ==l.4312) is obtained in 79% yield. Substantially the same yield is obtained in another example when the temperature oi the solution during the addition ot beta-propiolactone is 25 to 30 C.

Examples 6 to 8 d The procedure of Example 3 is again three times repeated using methanol, n-propanol and 2-ethyl hexanol, respectively, in place of ethanol. Good yields of methyl beta-chloro propionate (B.

P. 72.5-74 C./56 mm.); n-propyl beta-chloro-' propionate (B; P. 76.8485/12 mm.; Nb-=1.4281) and Z-ethylhexyl beta-chloropropionate (B. P. l20-l23 J4 mm; N '=1.4430), respectively, are obtained. 1

Examples Q 72 grams of beta-proplolacetone are dissolved in 300 ml. or commercial ethanol and hydrogen bromide is added to the solution for five hours at atemperatuze of about 24 C. The reaction mixture is then distilled under reduced pressure whereupon a fraction consisting of 125.6 g. (69.4%) of ethyl beta-bromopropionate (B. P. 1055-1085 C./55 min.) is obtained.

In the above examples the alcohol employed is an allqrl alcohol and the products obtained are alkyl esters of beta-halo jpropionic acids. Such esters are easily converted to alkyl acrylates by treatment with alkali metal hydroxides asis dis- J closed in U. S. Patent 1,864,884 to Bauer, 'or by treatment with strong acids as is disclosed in U; S. Patent 1,945,613 to Jacobi et a1. Such treatments may be applied directly to the reaction mixture, without isolating the ester and the mixture-then distilled to yield the corresponding alkyl acrylate. This invention thus provides a convenientand economical route tothe highly useiul alkyl acrylates. 'In addition, to the .alkyl alcohols specifically used in the examples any other suchalcohol including isopropyl alcoh'ol, tert-butyl alcohol, the various amyi, hexyl, heptyl, octyl,

, docyl, and dodecyl alcohols and'the like may also be employed to yield other alkyl beta-halo propiilliates...

' However, the invention is not confined to the preparation of alkyl beta-halo propionates, but rath'er other embodiments are embraced within its generic scope. Monohydrie alcohols; other than allqrl alcohols which may be used include ethyl ether (Carbitoll;betaethoxye allyl alcohol and other unsaturated aliphatic monohydric alcohols; cyclohexanol and other allcyclic monohydric alcohols; benzyl alcoh other aromatic alcohols; iurfuryl alcoho hydrofurfuryl alcohol, diethylene. 1y

'1 losol've) or a similar monohydric alcohol composed of carbon, hydrogen and oxygen and having all its hydrogen attached to carbon except for the hydrogen of the alcoholic hyldroxyl group. When such alcohols are reacted with beta-propiolactone and hydrogen chloride, for example.

the corresponding esters of beta-chloropropionic acid areobtained;

Polyhydric alcohols such as ethylene glycol, di-

ethylene glycol, glycerol and the like may also be reacted with beta-lactones and hydrogen halides according to this invention. For example, when ethylene glycol, beta-propiolactone and hydrogen chloride are used, the product first formed is ethylene glycol di-beta-chloropropionate which,

however, is unstable and may be dehydrochlorinated by distillation or by other. methods to liberate hydrogen chloride and thus produce ethylene glycol diacrylate.

Similarly, when an alcohol containing halogen substituted for hydrogen such eth'ylene chlorohydrin, glycerolalpha-chlorohydrin, trimethylene chlorohydrin, trimethylene bromohydrin, alphabeta glycerol dichlorohydrin; alpha-gamma glycerol dichlorohydrin or the like is used, the first 'formed product, an ester of a beta-halo acid with a, halo-alcohol, is often dehydrohalogenated on heating with the result, that an unsaturated ester is produced. I

The practice of the invention utilizing a haloalcohol is illustrated in the following examples.

Example 10 A solution is prepared by dissolving -144 grams Example 11 '72 grams of beta-propiolactone dissolved in 40 cc. of ethylene chlorohydrin are added to 140 cc.

of ethylene chlorohydrin while the latter is being heated to reflux temperature. Hydrogen chloride is then bubbled into the refluxing solution (temperature of IOU-120 Qlfor a period of 6 hours. The reaction mixture is washed with water toremove excess hydrogen chloride and is then distilled under reduced pressure, decomposition oc curring with liberation of hydrogen chloride. Up-

on redistillation, a fraction consisting of a30% yield of 2-chloroethyl acrylate (B. P. 3943 C./3 mm.) together with some higher boiling material is obtained. r a a The 2-chloroethyl acrylate produced in this example probably results from thedehydrochlorination at the higher temperature of 2-chloroethyl 2-betachloropropionate first formed. By more vigorous dehydrochlorinating conditions such as distilling the reactionproduct with decomposition at higher pressure, two molecules of hydrogen chloride may be liberated and vinyl acrylate thus Example 12 A solution of 144 grams ofbeta-propiolactone in 300 cc. of alpha-gamma glycerol dichlorohydrin (1,3-dichloroisopropanol) is cooled to -15 C. and, while maintaining this temperature gaseous hydrogen chloride is passed into the solution for about 8 hours. The reaction mixture is then pbured into ice water, the oily layer separated, washed with water to remove excess HCl and In addition to the alcohols mentioned hereinabove other alcohols may also be reacted with a beta-lactone and a hydrogen halide in accordance with this invention. Thus, nitro-substituted alcohols such as 2-nitro ethanol and the like may be used. Preferably the alcohol is one in which all hydrogen atoms except those attached to carbon arepresent in alcoholic hydroxyl groups, but alcohols containing hydrogen in substituent groups such as lactic acid (which is a carboxysubstituted alcohol) and the like, methylol urea, beta-mercaptc ethanol and the like are also operable.

Beta-propiolactone, the simplest possible betalactone, is the preferred beta-lactone for use in this invention because of'its low cost and the particular value of the products obtained. However, the use of beta-isobutyrolactone, one of the homologs of beta-propiolactone, is also advantageous since the reaction then leads to esters of beta-halo-iso-butyric acid, which yield methacrylates on dehydrohalogenation. Other homologs of beta-propiolactone, that is, other beta-lactones of saturated aliphatic monocarboxylic acids, such as beta-n-butyrolactone, betavalerolactone, beta iso-valerolactone, beta-ncaprolactone, alpha ethyl beta-propiolactone, alpha-isopropyl-beta-propiolactone, alpha-butylbeta-propiolactone, alpha-methyl-beta butyrofrom aliphatic unsaturation) and may be pre pared in the manner described in U. 8. Patent 2,356,459 to Frederick E. Kllng. Still other known beta-lactones include lactones of unsaturated beta-hydroxy carboxylic acids, mono-beta 'lactones of dicarboxylic acidsand dilactones of dicarboxylic acids in which at least one of the lactones is' beta, examples of which are alpha,alphadimethyl-beta propiolactone beta carboxylic acid; trimethyl-beta-propiolactone beta carboxylic acid; beta,beta-dimethyl-beta-propiolactone-alpha-carboxylic acid; trimethyl-beta-prolactone, alpha-ethyl-beta-butyrolactone, betapiolactone-alpha-carboxylic acid and the betadelta-dilactone of citrylidene malonic acid, all of which like the beta-lactones before mentioned are composed exclusively of hydrogen, carbon and carbonoxy oxygen atoms. In addition to these compounds other compounds containing the structure but having the valences on the alpha and beta. carbons attached to groups containing elements other than or in addition to carbon and hydrogen such as oxygen, nitrogen, sulfur and halogen, whether in essentially unreactive structure such as nitro groups and ether linkages or in radicals containing reactive hydrogen such as amino and lactones may be usd in the practice of this invention.

Numerous other modifications and variations in the invention as herein described will be apparent to those skilled in the art and are within the spirit and scope of the appended claims.

We claim:

1. The method which comprises bringing into reactive contact with one another in the liquid phase, a beta-lactone, an alcohol and an acid consisting of a hydrogen halide, whereupon reaction occurs to form a beta-halo carboxylic acid ester.

2. The method which comprises forming a solution of a saturated aliphatic beta-lactone in a molecular excess of an alcohol which is liquid under normal conditions and bringing an acid consisting of a hydrogen halide into reactive contact with the said alcohol at a temperature at which the said alcohol is liquid; whereupon reaction occurs to form a beta-halo carboxylic acid ester.

3. The method which comprises forming a solution of beta-propiolactone in a molecular excess of a monohydric alcohol which is liquid under normal conditions and bringing a molecular excess of an acid consisting of a hydrogen halide into reactive contact with the said alcohol at a temperature at which the said alcohol is liquid, whereupon reaction occurs to form a betahalo propionic acid ester.

4. The method .of preparing an alkyl ester of a beta-halo propionic acid which comprises bringing a molecular excess oi. acid consisting of hydrogen halide into reactive contact with a solution containing a molecular equivalent of beta-propiolactone dissolved in a molecular excess or an alkyl alcohol which is liquid under normal conditions, at a temperature at which the said alcohol is liquid, whereupon reaction occurs to form an alkyl ester of a beta-halo propionic acid and separating the ester thus formed.

5. The method 0! claim 4 wherein the hydrogen halide is hydrogen chloride and the alcohol is ethanol, the ester formed being ethyl betachloro propionate. I

6. The method of claim 4 wherein the hydrogen halide is hydrogen chloride and the alcohol is n-butanol, the ester formed being n-butyl betachloro propionate.

7. The method of preparing alkyl esters 01 betachloro propionic acid which comprises'dissolving beta-propiolactone in a molecular excess of a liquid alkyl alcohol, adding a molecular excess acid consisting o1 gaseous hydrogen chloride to the solution at a temperature of Q to 20 0., and separating the alkyl ester of beta-chloro propionic acid thus formed.

8. The method of preparing ethyl beta-chloro fpropionate which comprises forming a solution of beta-propiolactone in a molecular excess or ethanol, saturating the solution with gaseous hydrogenchioride at a temperature of about 0 to 8 20% 0., refluxing the solution and then distilling the solution to yield ethyl beta-chloro propionate.

9. The method which comprises bringing into reactive contact with one another in the liquid phase, heta-propiolactone. a halogen containing aliphatic alcohol and a hydrogen halide, whereupon reaction occurs to form an ester of betachloro propionic acid with thehalo alcohol, and then distilling the reaction product, whereupon dehydrohalogenation o! the said ester occurs to produce an acrylic acid ester.

10. The method of claim 9 wherein the alcohol is ethylene chlorohydrin and the hydrogen halide is hydrogen chloride.

THOMAS L. GRESHAM. FORREST W. SHAVER.

REFERENCES CITED The following references are of record in the file oi this patent:

UNITED STATES PATENTS OTHER REFERENCES Beilstein, Hand. der Organ. Chem., vol. 2 (2nd suppl.), p. 227, 4th ed.

Certificate of Correction Patent No. 2,422,728. June 24, 1947. THOMAS L. GRESHAM ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 3, line 43, for betapropiolacetone read beta-propiolactone; column 4, line 10, for hyldroxyl read hydroxyl; line 27, after such insert as; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 28th day of October, A. D. 1947.

[SEAL] THOMAS F. MURPHY,

Assistant Uommz'ssz'oner of Patents. 

